Sulfur- and Nitrogen-Doped, Ferrocene-Derived Mesoporous Carbons with Efficient Electrochemical Reduction of Oxygen

ABSTRACT: Development of inexpensive and sustainable cathode catalysts that can efficiently catalyze the oxygen reduction reaction (ORR) is of significance in practical application of fuel cells. Herein we report the synthesis of sulfur and nitrogen dual-doped, ordered mesoporous carbon (SN-OMCs), which shows outstanding ORR electrocatalytic properties. The material was synthesized from a surface-templating process of ferrocene within the channel walls of SBA-15 mesoporous silica by carbonization, followed by in situ heteroatomic doping with sulfur- and nitrogen-containing vapors. After etching away the metal and silica template, the resulting material features distinctive bimodal mesoporous carbon frameworks with high nitrogen Brunauer−Emmett−Teller specific surface area (of up to ∼1100 m2/g) and uniform distribution of sulfur and nitrogen dopants. When employed as a noble-metal-free electrocatalyst for the ORR, such SN-OMC shows a remarkable electrocatalytic activity; improved durability and better resistance toward methanol crossover in oxygen reduction can be observed. More importantly, it performs a low onset voltage and an efficient nearly complete four-electron ORR process very similar to the observations in commercial 20 wt % Pt/C catalyst. In addition, we also found that the textural mesostructure of the catalyst has superseded the chemically bonded dopants to be the key factor in controlling the ORR performance